Azo dyes from unsubstituted or substituted 3-amino-pyridine and aryl or heterocyclic couplers

ABSTRACT

Azo dyes having the general formula ##STR1## in which each of X, Y and Z are independently selected from H and a variety of substituents, preferably provided that at least one of X and Y is a substituent selected, for example, from --CN, halogen, alkyl, and alkylsulfonyl, and C is the residue of a phenol, naphthol, indole, imidazothiazole, pyrazolone, thiazole, isothiazole or pyrazole type disperse dye coupling component. These dyes which are unexpectedly non-phototropic produce yellow to orange shades on hydrophobic fibers and exhibit improvements in one or more properties such as dyeability, dye exhaustion rate, light fastness, nonblooming, pH stability, build, fastness to ozone and nitrogen oxide, crock and wash fastness, migration, transfer, and pH stability on polyester, polyamide and other fibers including cellulose ester.

DESCRIPTION

This invention concerns azo dyes having the general formula ##STR2## in which each of X, Y and Z are independently selected from H and a variety of substituents defined below, preferably provided that at least one of X and Y is a substituent selected, for example, from --CN, halogen, alkyl, and alkylsulfonyl, and C is the residue of a phenol, naphthol, indole, imidazothiazole, pyrazolone, thiazole, isothiazole or pyrazole type disperse dye coupling component. These dyes which are unexpectedly non-phototropic produce yellow to orange shades on hydrophobic fibers and exhibit improvements in one or more properties such as dyeability, dye exhaustion rate, light fastness, nonblooming, pH stability, build, fastness to ozone and nitrogen oxide, crock and wash fastness, migration, transfer, and pH stability on polyester, polyamide and other fibers including cellulose ester, over such dyes as are disclosed in British Patent No. 1,497,095.

The couplers C useful in the present invention have the formulae ##STR3## wherein: for couplers I through V as appropriate, R² and R¹⁴ each represents hydrogen or up to three substituents selected from fluorine, chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals having the formula --NH--X--R³ in which X is --CO--, --COO--, or --SO₂ and R³ is selected from alkyl and alkyl substituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO-- in the formula --NH--X--R³, R³ also is selected from hydrogen, amino, alkylamino, dialkylamino, arylamino, aryl, and furyl;

R⁴ is selected from hydrogen, alkyl, aryl, and cycloalkyl;

R⁹, R¹⁰ and R¹¹ are each selected from hydrogen, alkyl, phenyl, phenyl substituted with 1-3 substituents selected from Cl, Br, alkyl and alkoxy, alkylthio, benzylthio, cyclohexylthio, phenylthio and phenylthio substituted as for the phenyl;

e is 1 or 2;

each of the aliphatic portions or moieties of the above alkyl, cycloaliphatic, alkoxy, alkanoyl and like groups, as well as the aryl and aryloxy groups, may be substituted further with 1-3 of the following: hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono; cyclohexyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl; benzoylsulfonicimidyl; alkylsulfonamido; phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl; alkoxycarbonyloxy; ##STR4## wherein Y is --NH--, --NH--alkyl--, --O--, --S--, or --CH₂ O--; --S--R⁶ wherein R⁶ is alkyl, phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, or ##STR5## --OXR³ ; --NH--X--R³ ; --X--R³ ; --CONR⁷ R⁷ ; --SO₂ NR⁷ R⁷ ; wherein R³ and X are as defined above and each R⁷ is selected from H and R³ ; alkoxy; alkoxy substituted with 1-3 of hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy; phenoxy substituted with 1-3 of alkyl, alkoxy or halogen;

for Couplers VI, VII and VIII,

R¹ and R² each is H, alkyl, cyclohexyl, alkyl substituted cyclohexyl, aryl or alkyl substituted with aryl;

R³ is H, alkyl, lower alkyl substituted with 1-3 of halogen, hydroxy, aryl or lower alkanoyloxy, cyclohexyl, lower alkyl substituted cyclohexyl, or allyl; and

R² and R³ collectively are pentamethylene or ethyleneoxyethylene;

in which each aryl group is phenyl or phenyl substituted with 1-3 of alkyl, hydroxyalkyl, alkoxy, hydroxy, halogen, cyclohexoxy, cyclohexylmethyl, alkanoylamino, nitro or alkoxycarbonyl;

X, Y, and Z of the pyridine ring are independently selected from hydrogen, halogen, alkyl, alkoxy, aryl, cyano, carbamoyl, CONHR₁₂, CONR₁₂ R₁₃, SO₂ R₁₂, COOR₁₂, sulfamoyl, SO₂ NHR₁₂, SO₂ NR₁₂ R₁₃, formyl, nitro, SCN, and SR₁₄, wherein R₁₂ is alkyl, cycloalkyl, or aryl, each of which cycloalkyl and aryl R₁₂ groups may be substituted with --CN, alkoxy, alkyl, hydroxy, alkanoyl or alkanoyloxy, R₁₃ is alkyl which may be substituted with cycloalkyl, or aryl, each of which substituents on R₁₃ may itself be substituted with --CN, alkoxy, alkyl, hydroxy, alkanoyl or alkanoyloxy, and R₁₄ is selected from R₁₂ and heterocyclic radicals, preferably ##STR6## pyridyl, pyrimidinyl, and 1,3,4-thiadiazol-2-yl, wherein R⁷ is as defined above, and preferably at least one of X and Y is cyano, SO₂ R₁₂, SR₁₄, halogen, carbalkoxy, formyl, or nitro;

and wherein all of the aliphatic portions or moieties of all of the above groups within the definitions of X, Y, Z and the couplers, e.g the alkyl portions of alkoxy and alkylamino, contain from 1-8 carbons and are straight or branched.

Preferred dyes of the present invention have the formula ##STR7## wherein X is chlorine, bromine, cyano, alkylthio, alkylsulfonyl, arylsulfonyl or --S heterocycle; C is selected from ##STR8## wherein the ring is substituted in the 4 position with alkyl, alkoxy or halogen; ##STR9## wherein the naphthalene ring is unsubstituted; ##STR10## wherein R⁹ is alkyl or aryl, R⁴ is hydrogen, alkyl or cyanoethyl, and the benzene ring is unsubstituted; ##STR11## wherein R⁹ is phenyl, and R¹⁰ is hydrogen or methyl; ##STR12## wherein R⁴ is hydrogen or alkyl and R¹¹ is alkyl or phenyl; ##STR13## wherein R¹ is phenyl, R² is hydrogen or alkyl and R³ is alkyl or aryl, ##STR14## wherein R¹ is alkyl; and ##STR15## wherein R¹ is alkyl and R² is hydrogen or alkyl.

Most preferred dyes of the present invention have the formula ##STR16##

This invention will be further illustrated by the following examples although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention.

In general, the dyes are prepared by diazotizing 3-aminopyridines and then coupling, however, certain dyes are best prepared by nucleophilic substitution on the corresponding halopyridylazo dyes I as follows: ##STR17##

For example, Dyes I may be reacted with cuprous cyanide or sodium dicyanocuprate to produce the 2-cyano derivatives (II). Alkali metal mercaptides and sulfinates react with dyes I to give sulfides (III) and sulfones (IV), respectively. Displacements are also possible with nitrites, alkoxides, phenoxides, and sulfites to produce dyes containing nitro, alkoxy, phenoxy, and sulfo groups, respectively.

For each of the above reactions the temperature may vary within a wide range depending on the nature of the organic medium and, in particular, on the heat stability of the starting dyestuff. In general, the temperature should be maintained between about 25° and 150° C., with between 25° and 100° C. being preferred. Suitable solvents which may be readily selected by one skilled in the art include, for example, dimethylsulfoxide, formamide, dimethylformamide, dimethylacetamide, N-methyl-pyrrolidone, pyridine, quinoline, acetonitrile, benzonitrile and phosphoric acidtrisdimethylamide. Catalysts such as cupropus bromide and the like, also well known to the art, may be employed. The dye reactant may be the --Cl, --Br, --I or --F intermediate, and the displaced halogen in each of these reactions may be taken up by a cation, e.g., Na⁺, K⁺, or the like which may be present in a reactant, e.g., NaCu(CN)₂, or added thereto, such as K₂ CO₃ or sodium acetate, in sufficient amount to maintain the desired neutral or basic reaction system. Typical sulfinic compounds are CH₃ SO₂ Na, PhSO₂ Na and typical mercaptans are C₂ H₅ -SH and Ph-SH. These reactants, of course, have the respective general formulae R₁₂ SO₂ M where, e.g., M is Na⁺, K⁺, or the like, and HSR₁₄ where R₁₂ and R₁₄ are defined above.

The practice of the invention is illustrated further by the following examples:

EXAMPLES 1-10 Diazotization and Coupling of 3-Aminopyridine

3-Aminopyridine (0.1 m) is dissolved in 100 ml. of water containing 30 ml. concentrated HCl. The solution is cooled and a solution of 7.1 g. of NaNO₂ in 20 ml. of water is added at 0°-5° C. After stirring for about 15 minutes, the diazonium salt is coupled with the following couplers:

Example 1-2-Phenylindole;

Example 2-N-Methyl-2-phenylindole;

Example 3-N-2-Carbamylethyl-2-phenylindole;

Example 4-6-Phenylimidazo[2,1-b]thiazole;

Example 5-2-(N,N-Diethylamino)-4-phenylthiazole;

Example 6-2-(N-Methyl-N-phenylamino)-4-phenylthiazole;

Example 7-5-Amino-3-methylisothiazole;

Example 8-5-Amino-3-t-butylpyrazole;

Example 9-5-Amino-3-methyl-N-phenylpyrazole; and

Example 10-5-Amino-3-methyl-N-2-hydroxyethylpyrazole.

The coupling is done as follows: Each of the above couplers (0.01 mole) is dissolved in 25-50 ml. of 1:5 acid (1 part propionic acid:5 parts acetic acid). To the chilled solution of each coupler is added a 0.01 mole aliquot of the above diazonium solution. The mineral acid is neutralized by the addition of solid ammonium acetate. Water is added to precipitate the dyes which are collected by filtration, washed with water and dried in air. If needed, the dyes are purified by reslurrying in hot methanol or ethanol.

EXAMPLES 11-20 Diazotization and Coupling of 3-Amino-2-chloropyridine

3-Amino-2-chloropyridine (12.8 g, 0.1 mole) is dissolved in 100 ml. H₂ O and 30 ml. of concentrated HCl. The solution is cooled and a solution of 7.1 g. of NaNO₂ in 20 ml. of H₂ O is added at 0°-5° C. After being stirred at 0°-5° C. for 15 minutes, the diazonium salt was coupled to the following couplers:

Example 11-p-Cresol;

Example 12-2-Naphthol;

Example 13-m-Acetamidophenol;

Example 14-N-n-Butyl-3-hydroxy-2-naphthoicacid amide;

Example 15-3-Methyl-N-phenyl-5-pyrazolone;

Example 16-3,5-Diphenyl-5-pyrazolone;

Example 17-3-Methyl-5-pyrazolone;

The above couplers (0.01 m. of each) are dissolved in 25 ml. of water containing 1.6 g. of sodium hydroxide at room temperature. Ice is added thereto and then a 0.01 m. aliquot of the above diazonium salt. The pH is adjusted to about seven by addition of acetic acid. The dyes are collected by filtration, washed with water, and dried in air.

Dyeing of fiber material, according to the invention, is appropriately carried out from an aqueous suspension in the presence of carriers at between 80° and 100° C., in the absence of carriers between 100°-130° C., or using the so-called thermofixing process at 180°-230° C. Printing of textile materials can be carried out by steaming the goods, printed with the present dyes in the presence of a carrier at temperatures between 80° and 110° C. or in the absence of a carrier at 110°-140° C., or also by treating the printed goods according to said thermofixing process.

A typical general procedure by which polyester, e.g., poly(ethylene terephthalate) can be dyed with the present dyes is as follows: The dye cake is dispersed by heating and agitating a dyepot containing the dye cake and methyl Cellosolve. When the dyecake has been ground free of lumps and dissolved as much as possible in the methyl Cellosolve, 2% based on weight of the fabric of Igepon T-51 and 2.0% based on weight of the fabric of sodium lignin sulfonate from a premixed solution of the two components is added. Sufficient demineralized water is added to make about a 30:1 bath ratio of water to dye and a small amount of Versene 100 (sodium salt of ethylenediaminetetracetic acid) and Tanalon JDM-72 (dye carrier) are added. The pH of the dyebath is adjusted to about 5.0 with acetic acid. The fabric samples (wet-out) are entered into the dyepot and the entire contents thereof entered into a pressure dyeing container. The container is sealed and entered into a High Temperature Launder-Ometer which is heated to 49° C. and rotation thereof started. The temperature of the Launder-Ometer is raised to 129° C. at the rate of about 2.8° C. per minute, and maintained at this temperature for 1 hour. The Launder-Ometer is then cooled, and the fabric samples removed and scoured in demineralized water containing 1 g./l. of neutral soapand 1 g./l. of sodium carbonate. The samples are rinsed in cold demineralized water and dried at 121° C. in a forced air oven.

The following tables show additional exemplary dyes of the present invention.

                                      TABLE 1                                      __________________________________________________________________________      ##STR18##                                                                     X               Y       Z          R.sup.9  R.sup.2   R.sup.4                  __________________________________________________________________________     H               H       H          C.sub.6 H.sub.5                                                                         H         CH.sub.3                 CH.sub.3        H       H          CH.sub.3 6-CH.sub.3                                                                               CH.sub.3                 CN              H       H          CH.sub.3 6-CH.sub.3                                                                               C.sub.6 H.sub.5          SCH.sub.3       Cl      H          CH.sub.3 H         C.sub.2 H.sub.5          CN              H       H          C.sub.6 H.sub.5                                                                         H         H                        CN              Br      H          C.sub.6 H.sub.5                                                                         H         CH.sub.3                 Cl              NO.sub.2                                                                               4-Br       CH.sub.3 H         CH.sub.3                 Br              CHO     4-Br       CH.sub.3 5-OC.sub.2 H.sub.5                                                                       CH.sub.3                 SO.sub.2 CH.sub.3                                                                              CN      5-SO.sub.2 CH.sub.3                                                                       CH.sub.3 5-OC.sub.2 H.sub.5                                                                       H                        SO.sub.2 CH.sub.3                                                                              H       4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.4p-Br                                                                     H         H                        SO.sub.2 CH.sub.3                                                                              H       4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                         H         C.sub.2 H.sub.4                                                                CONH.sub.2               SO.sub.2 C.sub.6 H.sub.5                                                                       H       H          C.sub.6 H.sub.4p-OCH.sub.3                                                              H         C.sub.2 H.sub.4 CN       SC.sub.2 H.sub.4 OH                                                                            I       H          C.sub.6 H.sub.4p-OCH.sub.3                                                              5-C.sub.6 H.sub.11                                                                       C.sub.2 H.sub.4                                                                SO.sub.2 NH.sub.2        SC.sub.6 H.sub.5                                                                               H       4-Cl       C.sub.2 H.sub.4 CN                                                                      6-OC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4                                                                N(COCH.sub.3).sub.2                                                            6                        SO.sub.2 C.sub.6 H.sub.5                                                                       H       4-SO.sub.2 C.sub.6 H.sub.5                                                                C.sub.2 H.sub.4 OCOCH.sub.3                                                             6-SCH.sub.3                                                                              C.sub.2 H.sub.4                                                                SO.sub.2 NHC.sub.2                                                             H.sub.5                  CN              SCH.sub.3                                                                              4-CN       CH.sub.3 6-SC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4                                                                SO.sub.2 NHC.sub.2                                                             H.sub.5                  CH.sub.3        NO.sub.2                                                                               H          CH.sub.3 6-NHCOOCH.sub.3                                                                          C.sub.2 H.sub.4 OH       CN              H       H          C.sub.3 H.sub.7                                                                         6-NHSO.sub.2 CH.sub.3                                                                    C.sub.2 H.sub.4 CN       OCH.sub.3       SO.sub.2 CH.sub.3                                                                      H          CH.sub.3 6-OCH.sub.3                                                                              C.sub.2 H.sub.4                                                                OCOCH.sub.3              SC.sub.6 H.sub.4m-CH.sub.3                                                                     SC.sub.6 H.sub.5                                                                       H          CH.sub.3 5-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4                                                                OCOCH.sub.3              CN              H       H          C.sub.2 H.sub.5                                                                         6-NHCOCH.sub.2 Cl                                                                        C.sub.6 H.sub.13         C.sub.6 H.sub.5 SC.sub.6 H.sub.11                                                                      H          C.sub.2 H.sub.5                                                                         6-NHCOC.sub.2 H.sub.4                                                                    C.sub.2 H.sub.4 OH       CN              H       H          C.sub.2 H.sub.5                                                                         6-NHCOC.sub.2 H.sub.4                                                                    CH.sub.2 C.sub.6                                                               H.sub.5                  CN              H       4-CN       C.sub.2 H.sub. 5                                                                        6-NHCONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CN       CONH.sub.2      CN      4-CN       C.sub.6 H.sub.4p-OCH.sub.3                                                              6-NHCON(C.sub.2 H.sub.5).sub.2                                                 6         C.sub.2 H.sub.5          CONHC.sub.2 H.sub.5                                                                            CN      4-CN       C.sub.2 H.sub.5                                                                         6-CH.sub.3                                                                               C.sub.2 H.sub.4                                                                NHCOCH.sub.3             CON(C.sub.2 H.sub.5).sub.2                                                                     CN      4-CN       C.sub.2 H.sub.5                                                                         6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4                                                                CONH.sub.2               CN              H       4-CN       CH.sub.3 H         C.sub.2 H.sub.4                                                                NHCOCH.sub.3             CN              SO.sub.2 CH.sub.3                                                                      4-CN       CH.sub.3 H         C.sub.2 H.sub.4 Cl       SO.sub.2 CH.sub.3                                                                              H       4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.4p-CH.sub.3                                                               6-OH      C.sub.2 H.sub.4 Cl       SO.sub.2 N(CH.sub.3 ).sub.2                                                                    SO.sub.2 C.sub.6 H.sub.5                                                               4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                         H         H                        SO.sub.2 C.sub.4 H.sub.9n                                                                      H       4-SO.sub.2 C.sub.4 H.sub.9n                                                               C.sub.6 H.sub.5                                                                         H         H                        SC.sub.2 H.sub.4 OH                                                                            H       4-SC.sub.2 H.sub.4 OH                                                                     C.sub.6 H.sub.5                                                                         H         H                        NO.sub.2        CO.sub.2 CH.sub.3                                                                      5-CO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.53                                                                        H         H                        SCH.sub.3       CO.sub.2 C.sub.2 H.sub.5                                                               5-CN       C.sub.6 H.sub.5                                                                         H         H                        CHO             CO.sub.2 C.sub.2 H.sub.5                                                               5-CN       C.sub.6 H.sub.5                                                                         H         H                        COOCH.sub.3     H       4-OC.sub.2 H.sub.5                                                                        C.sub.6 H.sub.5                                                                         H         CH.sub.3                 H               CN      5-CN       CH.sub.3 6-CH.sub.3                                                                               CH.sub.3                 SO.sub.2 C.sub.6 H.sub.5                                                                       H       4-SO.sub.2 C.sub.6 H.sub.5                                                                CH.sub.3 6-CH.sub.3                                                                               C.sub.6 H.sub.5          SO.sub.2 C.sub.6 H.sub.5                                                                       H       4-CH.sub.3 CH.sub.3 H         C.sub.2 H.sub.5          SO.sub.2 C.sub.6 H.sub.4p-Cl                                                                   H       4-SO.sub.2 C.sub.6 H.sub.4p-Cl                                                            C.sub.6 H.sub.5                                                                         H         H                        SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                             H       4-SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                      C.sub. 6 H.sub.5                                                                        H         CH.sub.3                 SO.sub.2 C.sub.6 H.sub.4m-OCH.sub.3                                                            SO.sub.2 C.sub.6 H.sub.11                                                              4-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                     CH.sub.3 H         CH.sub.3                 SO.sub.2 CH.sub.2 CH.sub.2 CN                                                                  H       4-SO.sub.2 CH.sub.2 CH.sub.2 CN                                                           CH.sub.3 5-OC.sub.2 H.sub.5                                                                       CH.sub.3                 SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              H       4-SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                       CH.sub.3 5-OC.sub.2 H.sub.5                                                                       H                         ##STR19##      s-pyridyl                                                                               ##STR20## C.sub.6 H.sub.4p-Br                                                                     H         H                        SC.sub.6 H.sub.11                                                                              H       4-SC.sub.6 H.sub.11                                                                       C.sub.6 H.sub.5                                                                         H         C.sub.2 H.sub.4                                                                CONH.sub.2                ##STR21##      NO.sub.2                                                                               H          C.sub.6 H.sub.4p-OCH.sub.3                                                              H         C.sub.2 H.sub.4 CN        ##STR22##      s-pyrimidinyl                                                                          H          C.sub.6 H.sub.4p-OCH.sub.3                                                              5-C.sub.6 H.sub.11                                                                       C.sub.2 H.sub.4                                                                SO.sub.2 NH.sub.2         ##STR23##      CN      H          C.sub.2 H.sub.4 CN                                                                      6-OC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4                                                                N(COCH.sub.3).sub.2                                                            .                         ##STR24##      CN                                                                                      ##STR25## C.sub.2 H.sub.4 OCOCH.sub.3                                                             6-SCH.sub.3                                                                              C.sub.2 H.sub.4                                                                SO.sub.2 NHC.sub.2                                                             H.sub.5                   ##STR26##      COOCH.sub.3                                                                            H          CH.sub.3 6-SC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4                                                                SO.sub.2 NHC.sub.2                                                             H.sub.5                   ##STR27##      CN      H          CH.sub.3 6-NHCOOCH.sub.3                                                                          C.sub.2 H.sub.4 OH        ##STR28##      CN      H          C.sub.3 H.sub.7                                                                         6-NHSO.sub.2 CH.sub.3                                                                    C.sub.2 H.sub.4 CN       NO.sub.2        H       H          CH.sub.3 6-OCH.sub.3                                                                              C.sub.2 H.sub.4                                                                OCOCH.sub.3              CN              H       4-CN       CH.sub.3 5-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4                                                                OCOCH.sub.3              SO.sub.2 CH.sub.2 CH.sub.3                                                                     H       4-SO.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                         6-NHCOCH.sub.2 Cl                                                                        C.sub.6 H.sub.13         SO.sub.2 NHCH.sub.3                                                                            H       4-SO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                         6-NHCOC.sub.2 H.sub.4                                                                    C.sub.2 H.sub.4 OH       SO.sub.2 CH.sub.3                                                                              H       4-SO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                         6-NHCOC.sub.2 H.sub.4                                                                    CH.sub.2 C.sub.6                                                               H.sub.5                  SO.sub.2 C.sub.6 H.sub.5                                                                       H       4-SO.sub.2 C.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                         6-NHCONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CN       CN              H       4-Cl       C.sub.6 H.sub.4p-OCH.sub.3                                                              6-NHCON(C.sub.2 H.sub.5).sub.2                                                           C.sub.2 H.sub.5          SCN             NO.sub.2                                                                               4-Cl       C.sub.2 H.sub.5                                                                         6-CH.sub.3                                                                               C.sub.2 H.sub.4                                                                NHCOCH.sub.3             CN              H       4-Br       C.sub.2 H.sub.5                                                                         6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4                                                                CONH.sub.2               s-pyridyl       CHO     4-OCH.sub.3                                                                               CH.sub.3 H         C.sub.2 H.sub.4                                                                NHCOCH.sub.3             CN              H       4-CN       CH.sub.3 H         C.sub.2 H.sub.4 Cl       s-pyrimidinyl   H       4-CN       C.sub.6 H.sub.4p-CH.sub.3                                                               6-OH      C.sub.2 H.sub.4 Cl       CN              CH.sub.3                                                                               4-CN       C.sub.6 H.sub.5                                                                         H         H                        CN              Cl      4-CN       C.sub.6 H.sub.5                                                                         H         H                        CN              H       4-CONH.sub.2                                                                              C.sub.6 H.sub.5                                                                         H         H                        CN              H       4-CON(C.sub.2 H.sub.5).sub.2                                                              C.sub.6 H.sub.5                                                                         H         H                        CN              H       4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       C.sub.6 H.sub.5                                                                         H         H                        CN              H       4-SCN      C.sub.6 H.sub.5                                                                         H         H                        CN              H       4-SCH.sub.3                                                                               C.sub.6 H.sub.5                                                                         H         CH.sub.3                 SC.sub.6 H.sub.5                                                                               H       4-CN       CH.sub.3 6-CH.sub.3                                                                               CH.sub.3                 SC.sub.4 H.sub.9n                                                                              H       4-CN       CH.sub.3 6-CH.sub.3                                                                               C.sub.6 H.sub.5          CN              C.sub.6 H.sub.5                                                                        4-CN       CH.sub.3 H         C.sub.2 H.sub.5          CN              CN      4-CN       C.sub.6 H.sub.5                                                                         H         H                        NO.sub.2        H       H          C.sub.6 H.sub.5                                                                         H         CH.sub.3                 __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR29##                                                                     X               Y      Z          R.sup.9 R.sup.10                             __________________________________________________________________________     H               H      H          C.sub.6 H.sub.5                                                                        H                                    CH.sub.3        H      H          CH.sub.3                                                                               H                                    CN              H      H          CH.sub.3                                                                               H                                    SCH.sub.3       Cl     H          CH.sub.3                                                                               C.sub.6 H.sub.5                      CN              H      H          CH.sub.3                                                                               C.sub.6 H.sub.5                      CN              Br     H          C.sub.6 H.sub.5                                                                        CH.sub.3                             Cl              NO.sub.2                                                                              4-Br       C.sub.6 H.sub.5                                                                        CH.sub.3                             Br              CHO    4-Br       C.sub.6 H.sub.5                                                                        CH.sub.3                             SO.sub.2 CH.sub.3                                                                              CN     5-SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                               H                                    SO.sub.2 CH.sub.3                                                                              H      4-SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                               H                                    SO.sub.2 CH.sub.3                                                                              H      4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.4p-Br                                                                    H                                    SO.sub.2 C.sub.6 H.sub.5                                                                       H      H          C.sub.6 H.sub.4p-OCH.sub.3                                                             H                                    SC.sub.2 H.sub.4 OH                                                                            I      H          C.sub.6 H.sub.4p-OCH.sub.3                                                             Br                                   SC.sub.6 H.sub.5                                                                               H      4-Cl       C.sub.6 H.sub.4 CN                                                                     Br                                   SO.sub.2 C.sub.6 H.sub.5                                                                       H      4-SO.sub.2 C.sub.6 H.sub.5                                                                C.sub.2 H.sub.4 OCOCH.sub.3                                                            Br                                   CN              SCH.sub.3                                                                             4-CN       CH.sub.3                                                                               C.sub.2 H.sub.5                      CH.sub.3        NO.sub.2                                                                              H          CH.sub.3                                                                               C.sub.2 H.sub.5                      CN              H      H          C.sub.3 H.sub.7                                                                        C.sub.6 H.sub.5                      OCH.sub.3       SO.sub.2 CH.sub.3                                                                     H          CH.sub.3                                                                               C.sub.6 H.sub.5                      SC.sub.6 H.sub.4m-CH.sub.3                                                                     SC.sub.6 H.sub.5                                                                      H          C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4p-CH.sub.3            CN              H      H          C.sub.2 H.sub.5                                                                        H                                    C.sub.6 H.sub.5 SC.sub.6 H.sub.11                                                                     H          C.sub.2 H.sub.5                                                                        CONHC.sub.2 H.sub.5                  CN              H      H          C.sub.2 H.sub.5                                                                        CH.sub.3                             CN              H      4-CN       C.sub.6 H.sub.4p-OCH.sub.3                                                             C.sub.2 H.sub.5                      CONH.sub.2      CN     4-CN       C.sub.2 H.sub.5                                                                        SCN                                  CONHC.sub.2 H.sub.5                                                                            CN     4-CN       C.sub.2 H.sub. 5                                                                       CONH.sub.2                           CON(C.sub.2 H.sub.5).sub.2                                                                     CN     4-CN       CH.sub.3                                                                               CH(CH.sub.3).sub.2                   CN              H      4-CN       CH.sub.3                                                                               C.sub.6 H.sub.5                      CN              SO.sub.2 CH.sub.3                                                                     4-CN       C.sub.6 H.sub.4p-CH.sub.3                                                              C.sub.2 H.sub.5                      SO.sub.2 CH.sub.3                                                                              H      4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                        H                                    SO.sub.2 N(CH.sub.3).sub.2                                                                     SO.sub.2 C.sub.6 H.sub.5                                                              4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                        H                                    SO.sub.2 C.sub.4 H.sub.9n                                                                      H      4-SO.sub.2 C.sub.4 H.sub.9n                                                               C.sub.6 H.sub.5                                                                        H                                    SC.sub.2 H.sub.4 OH                                                                            H      4-SC.sub.2 H.sub.4 OH                                                                     C.sub.6 H.sub.5                                                                        H                                    NO.sub.2        CO.sub.2 CH.sub.3                                                                     5-CO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                        H                                    SCH.sub.3       CO.sub.2 C.sub.2 H.sub.5                                                              5-CN       C.sub.6 H.sub.5                                                                        H                                    CHO             CO.sub.2 C.sub.2 H.sub.5                                                              5-CN       C.sub.6 H.sub.5                                                                        H                                    COOCH.sub.3     H      4-OC.sub.2 H.sub.5                                                                        CH.sub.3                                                                               H                                    H               CN     5-CN       CH.sub.3                                                                               H                                    SO.sub.2 C.sub.6 H.sub.5                                                                       H      4-SO.sub.2 C.sub.6 H.sub.5                                                                CH.sub.3                                                                               C.sub.6 H.sub.5                      SO.sub.2 C.sub.6 H.sub.5                                                                       H      4-CH.sub.3 CH.sub.3                                                                               C.sub.6 H.sub. 5                     SO.sub.2 C.sub.6 H.sub.4p-Cl                                                                   H      4-SO.sub.2 C.sub.6 H.sub.4p-Cl                                                            C.sub.6 H.sub.5                                                                        CH.sub.3                             SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                             H      4-SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                      C.sub.6 H.sub.5                                                                        CH.sub.3                             SO.sub.2 C.sub.6 H.sub.4m-OCH.sub.3                                                            SO.sub.2 C.sub.6 H.sub.11                                                             4-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                     C.sub.6 H.sub.5                                                                        CH.sub.3                             SO.sub.2 CH.sub.2 CH.sub.2 CN                                                                  H      4-SO.sub.2 CH.sub.2 CH.sub.2 CN                                                           CH.sub.3                                                                               H                                    SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              H      4-SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                       CH.sub.3                                                                               H                                     ##STR30##      s-pyridyl                                                                              ##STR31## C.sub.6 H.sub.4p-Br                                                                    H                                    SC.sub.6 H.sub.11                                                                              H      4-SC.sub.6 H.sub.11                                                                       C.sub.6 H.sub.4p-OCH.sub.3                                                             H                                     ##STR32##      NO.sub.2                                                                              H          C.sub.6 H.sub.4p-OCH.sub.3                                                             Br                                    ##STR33##      s-pyrimidinyl                                                                         H          C.sub.6 H.sub.4 CN                                                                     Br                                    ##STR34##      CN     H          C.sub.2 H.sub.4 OCOCH.sub.3                                                            Br                                    ##STR35##      CN                                                                                     ##STR36## CH.sub.3                                                                               C.sub.2 H.sub.5                       ##STR37##      COOCH.sub.3                                                                           H          CH.sub.3                                                                               C.sub.2 H.sub.5                       ##STR38##      CN     H          C.sub.3 H.sub.7                                                                        C.sub.6 H.sub.5                       ##STR39##      CN     H          CH.sub.3                                                                               C.sub. 6 H.sub.5                     NO.sub.2        H      H          C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.4p-CH.sub.3            CN              H      4-CN       C.sub.2 H.sub.5                                                                        H                                    SO.sub.2 CH.sub.2 CH.sub.3                                                                     H      4-SO.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.5                                                                        CONHC.sub.2 H.sub.5                  SO.sub.2 NHCH.sub.3                                                                            H      4-SO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                        CH.sub.3                             SO.sub.2 CH.sub.3                                                                              H      4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.4p-OCH.sub.3                                                             C.sub.2 H.sub.5                      SO.sub.2 C.sub.6 H.sub.5                                                                       H      4-SO.sub.2 C.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                        SCN                                  CN              H      4-Cl       C.sub.2 H.sub.5                                                                        CONH.sub.2                           SCN             NO.sub.2                                                                              4-Cl       CH.sub.3                                                                               CH(CH.sub.3).sub.2                   CN              H      4-Br       CH.sub.3                                                                               C.sub.6 H.sub.5                      s-pyridyl       CHO    4-OCH.sub.3                                                                               C.sub.6 H.sub.4p-CH.sub.3                                                              C.sub.2 H.sub.5                      CN              H      4-CN       C.sub.2 H.sub.5                                                                        H                                    s-pyrimidinyl   H      4-CN       C.sub.6 H.sub.5                                                                        H                                    CN              CH.sub.3                                                                              4-CN       C.sub.6 H.sub.5                                                                        H                                    CN              Cl     4-CN       C.sub.6 H.sub.5                                                                        H                                    CN              H      4-CONH.sub.2                                                                              C.sub.6 H.sub.5                                                                        H                                    CN              H      4-CON(C.sub.2 H.sub.5).sub.2                                                              C.sub.6 H.sub.5                                                                        H                                    CN              H      4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       C.sub.6 H.sub.5                                                                        H                                    CN              H      4-SCN      CH.sub.3                                                                               H                                    CN              H      4-SCH.sub.3                                                                               CH.sub.3                                                                               H                                    SC.sub.6 H.sub.5                                                                               H      4-CN       CH.sub.3                                                                               C.sub.6 H.sub.5                      SC.sub.4 H.sub.9n                                                                              H      4-CN       CH.sub.3                                                                               C.sub.6 H.sub.5                      CN              C.sub.6 H.sub.5                                                                       4-CN       C.sub.6 H.sub.5                                                                        CH.sub.3                             CN              CN     4-CN       C.sub.6 H.sub.5                                                                        CH.sub.3                             NO.sub.2        H      H          C.sub.6 H.sub.5                                                                        CH.sub.3                             __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR40##                                                                     X              Y      Z          R.sup.4  R.sup.11                             __________________________________________________________________________     H              H      H          H        CH.sub.3                             CH.sub.3       H      H          H        C.sub.6 H.sub.4p-OCH.sub.3           CN             H      H          H        CF.sub.3                             SCH.sub.3      Cl     H          H        COOC.sub.2 H.sub.5                   CN             H      H          H        CONHC.sub.4 H.sub.9n                 CN             Br     H          H        C.sub.6 H.sub.5                      Cl             NO.sub.2                                                                              4-Br       C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.4p-Br                  Br             CHO    4-Br       C.sub.6 H.sub.5                                                                         C(CH.sub.3).sub.3                    SO.sub.2 CH.sub.3                                                                             CN     5-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.11                     SO.sub.2 CH.sub.3                                                                             H      4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.5                      SO.sub.2 CH.sub.3                                                                             H      4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5 SO.sub.2                                                                CH.sub.3                             SO.sub.2 C.sub.6 H.sub.5                                                                      H      H          C.sub.2 H.sub.5 SO.sub.2                                                                CH.sub.3                             SC.sub.2 H.sub.4 OH                                                                           I      H          CH.sub.3 CO                                                                             CH.sub.3                             SC.sub.6 H.sub.5                                                                              H      4-Cl       C.sub.6 H.sub.5 CO                                                                      CH.sub.3                             SO.sub.2 C.sub.6 H.sub.5                                                                      H      4-SO.sub.2 C.sub.6 H.sub.5                                                                CH.sub.3 CONH.sub.2                           CN             SCH.sub.3                                                                             4-CH       C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.5                      CH.sub.3       NO.sub.2                                                                              H          C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.5                      CN             H      H          C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.5                      OCH.sub.3      SO.sub.2 CH.sub.3                                                                     H          C.sub.6 H.sub.11                                                                        CF.sub.3                             SC.sub.6 H.sub.4m-CH.sub.3                                                                    SC.sub.6 H.sub.5                                                                      H          C.sub.2 H.sub.4 OH                                                                      C.sub.6 H.sub.4p-Cl                  CN             H      H          CH.sub.2 C.sub.6 H.sub.5                                                                CONHC.sub.2 H.sub.5                  C.sub.6 H.sub.5                                                                               SC.sub.6 H.sub.11                                                                     H          C.sub.2 H.sub.4 CN                                                                      CH(CH.sub.3).sub.2                   CN             H      H          C.sub.2 H.sub.5                                                                         CH(CH.sub.3).sub.2                   CN             H      4-CN       C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.2 H.sub.5                      CONH.sub.2     CN     4-CN       C.sub.2 H.sub.4 CONH.sub.2                                                              CH.sub.3                             CONHC.sub.2 H.sub.5                                                                           CN     4-CN       C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.2 H.sub.5                      CON(C.sub.2 H.sub.5).sub.2                                                                    CN     4-CN       C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.6 H.sub.5                      CN             H      4-CN       C.sub.6 H.sub.5                                                                         CH.sub.3                             CN             SO.sub.2 CH.sub.3                                                                     4-CN       C.sub.6 H.sub.5                                                                         CH.sub.3                             SO.sub.2 CH.sub.3                                                                             H      4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                         CH.sub.3                             SO.sub.2 N(CH.sub.3).sub.2                                                                    SO.sub.2 C.sub.6 H.sub.5                                                              4-SO.sub.2 CH.sub.3                                                                       C.sub.6 H.sub.5                                                                         CH.sub.3                             SO.sub.2 C.sub.4 H.sub.9n                                                                     H      4-SO.sub.2 C.sub.4 H.sub.9n                                                               C.sub.6 H.sub.5                                                                         CH.sub.3                             SC.sub.2 H.sub.4 OH                                                                           H      4-SC.sub.2 H.sub.4 OH                                                                     C.sub.6 H.sub.5                                                                         CH.sub.3                             NO.sub.2       CO.sub.2 CH.sub.3                                                                     5-CO.sub.2 CH.sub.3                                                                       H        CH.sub.3                             SCH.sub.3      CO.sub.2 C.sub.2 H.sub.5                                                              5-CN       H        C.sub.6 H.sub.4p-OCH.sub.3           CHO            CO.sub.2 C.sub.2 H.sub.5                                                              5-CN       H        CF.sub.3                             COOCH.sub.3    H      4-OC.sub.2 H.sub.5                                                                        H        COOC.sub.2 H.sub.5                   H              CN     5-CN       H        CONHC.sub.4 H.sub.9n                 SO.sub.2 C.sub.6 H.sub.5                                                                      H      4-SO.sub.2 C.sub.6 H.sub.5                                                                H        C.sub.6 H.sub.5                      SO.sub.2 C.sub.6 H.sub.5                                                                      H      4-CH.sub.3 C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.4p-Br                  SO.sub.2 C.sub.6 H.sub.4p-Cl                                                                  H      4-SO.sub.2 C.sub.6 H.sub.4p-Cl                                                            C.sub.6 H.sub.5                                                                         C(CH.sub.3).sub.3                    SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                            H      4-SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                      C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.11                     SO.sub.2 C.sub.6 H.sub.4m-OCH.sub.3                                                           SO.sub.2 C.sub.6 H.sub.11                                                             4-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                     C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.5                      SO.sub.2 CH.sub.2 CH.sub.2 CN                                                                 H      4-SO.sub.2 CH.sub.2 CH.sub.2 CN                                                           C.sub.6 H.sub.5 SO.sub.2                                                                CH.sub.3                             SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                             H      4-SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                       C.sub.2 H.sub.5 SO.sub.2                                                                CH.sub.3                              ##STR41##     s-pyridyl                                                                              ##STR42## CH.sub.3 CO                                                                             CH.sub.3                             SC.sub.6 H.sub. 11                                                                            H      4-SC.sub.6 H.sub.11                                                                       C.sub.6 H.sub.5 CO                                                                      CH.sub.3                              ##STR43##     NO.sub.2                                                                              H          CH.sub.3 CONH.sub.2                            ##STR44##     s-pyrimidinyl                                                                         H          C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.5                       ##STR45##     CN     H          C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.5                       ##STR46##     CN                                                                                     ##STR47## C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.5                       ##STR48##     COOCH.sub.3                                                                           H          C.sub.6 H.sub.11                                                                        CF.sub.3                              ##STR49##     CN     H          C.sub.2 H.sub.4 OH                                                                      C.sub.6 H.sub.4p-Cl                   ##STR50##     CN     H          CH.sub.2 C.sub.6 H.sub.5                                                                CONHC.sub.2 H.sub.5                  NO.sub.2       H      H          C.sub.2 H.sub.4 CN                                                                      CH(CH.sub.3).sub.2                   CN             H      4-CN       C.sub.2 H.sub.5                                                                         CH(CH.sub.3).sub.2                   SO.sub.2 CH.sub.2 CH.sub.3                                                                    H      4-SO.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.2 H.sub.5                      SO.sub.2 NHCH.sub.3                                                                           H      4-SO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.4 CONH.sub.2                                                              CH.sub.3                             SO.sub.2 CH.sub.3                                                                             H      4-SO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.2 H.sub.5                      SO.sub.2 C.sub.6 H.sub.5                                                                      H      4-SO.sub.2 C.sub.6 H.sub.5                                                                C.sub.2 H.sub.4 NHCOCH.sub.3                                                            C.sub.6 H.sub.5                      CN             H      4-Cl       C.sub.6 H.sub.5                                                                         CH.sub.3                             SCN            NO.sub.2                                                                              4-Cl       C.sub.6 H.sub.5                                                                         CH.sub.3                             CN             H      4-Br       C.sub. 6 H.sub.5                                                                        CH.sub.3                             s-pyridyl      CHO    4-OCH.sub.3                                                                               C.sub.6 H.sub.5                                                                         CH.sub.3                             CN             H      4-CN       C.sub.6 H.sub.5                                                                         CH.sub.3                             s-pyrimidinyl  H      4-CN       C.sub.6 H.sub.5                                                                         CH.sub.3                             CN             CH.sub.3                                                                              4-CN       H        CH.sub.3                             CN             Cl     4-CN       H        C.sub.6 H.sub.4p-OCH.sub.3           CN             H      4-CONH.sub.2                                                                              H        CF.sub.3                             CN             H      4-CON(C.sub.2 H.sub.5).sub.2                                                              H        COOC.sub.2 H.sub.5                   CN             H      4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       H        CONHC.sub.4 H.sub.9n                 CN             H      4-SCN      H        C.sub.6 H.sub.5                      CN             H      4-SCH.sub.3                                                                               C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.4p-Br                  SC.sub.6 H.sub.5                                                                              H      4-CN       C.sub.6 H.sub.5                                                                         C(CH.sub.3).sub.3                    SC.sub.4 H.sub.9n                                                                             H      4-CN       C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.11                     CN             C.sub.6 H.sub.5                                                                       4-CN       C.sub.6 H.sub.5                                                                         C.sub.6 H.sub.5                      CN             CN     4-CN       C.sub.6 H.sub.5 SO.sub.2                                                                CH.sub.3                             NO.sub.2       H      H          C.sub.2 H.sub.5 SO.sub.2                                                                CH.sub.3                             __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR51##                                                                                                         OH                                         X               Y       Z           Position                                                                            R.sup.2                               __________________________________________________________________________     H               H       H           2    5-CH.sub.3                            CN              H       H           2    5-CH.sub.3                            CN              H       H           2    5-OCH.sub.3                           SCH.sub.3       Cl      H           2    5-Cl                                  CN              H       H           2    5-Cl                                  CN              Br      H           4    3-OCH.sub.3                           Cl              NO.sub.2                                                                               4-Br        4    3-OCH.sub.3                           Br              CHO     4-Br        3,4  H                                     SO.sub.2 CH.sub.3                                                                              CN      5-SO.sub.2 CH.sub.3                                                                        4    2-NHC.sub.6 H.sub.5                   SO.sub.2 CH.sub.3                                                                              H       4-SO.sub.2 CH.sub.3                                                                        2    5-NHCOCH.sub.3                        SO.sub.2 CH.sub.3                                                                              H       4-SO.sub.2 CH.sub.3                                                                        3,4  H                                     SO.sub.2 C.sub.6 H.sub.5                                                                       H       H           2    5-CONHC.sub.4 H.sub.9n                SC.sub.2 H.sub.4 OH                                                                            I       H           2    5-C.sub.6 H.sub.11                    SC.sub. 6 H.sub.5                                                                              H       4-Cl        2    5-OC.sub.6 H.sub.5                    SO.sub.2 C.sub.6 H.sub.5                                                                       H       4-SO.sub.2 C.sub.6 H.sub.5                                                                 2    5-SCH.sub.3                           CN              SCH.sub.3                                                                              4-CN        2    5-SC.sub.6 H.sub.5                    CH.sub.3        NO.sub.2                                                                               H           2    5-NHCOOCH.sub.3                       CN              H       H           2    5-NHSO.sub.2 CH.sub.3                 OCH.sub.3       SO.sub.2 CH.sub.3                                                                      H           2    5-NHCOCH.sub.3                        SC.sub.6 H.sub.4m-CH.sub.3                                                                     SC.sub.6 H.sub.5                                                                       H           2    5-NHCOCH.sub.2 Cl                     CN              H       H           2    5-NHCOC.sub.2 H.sub.4 OH              C.sub.6 H.sub.5 SC.sub.6 H.sub.11                                                                      H           2    5-Cl                                  CN              H       H           2    5-NHCONHC.sub.2 H.sub.5               CN              H       4-CN        2    5-NHCON(C.sub.2 H.sub.5).sub.2        CONH.sub.2      CN      4-CN        2    5-CH.sub.3                            CONHC.sub.2 H.sub.5                                                                            CN      4-CN        2    5-NHCOCH.sub.3                        CON(C.sub.2 H.sub.5).sub.2                                                                     CN      4-CN        4    H                                     CN              H       4-CN        2    5-CH.sub.3                            CN              SO.sub.2 CH.sub.3                                                                      4-CN        2    5-CH.sub.3                            SO.sub.2 CH.sub.3                                                                              H       4-SO.sub.2 CH.sub.3                                                                        2    5-OCH.sub.3                           SO.sub.2 N(CH.sub.3).sub.2                                                                     SO.sub.2 C.sub.6 H.sub.5                                                               4-SO.sub.2 CH.sub.3                                                                        2    5-Cl                                  SO.sub.2 C.sub.4 H.sub.9n                                                                      H       4-SO.sub.2 C.sub.4 H.sub.9n                                                                2    5-Cl                                  SC.sub.2 H.sub.4 OH                                                                            H       4-SC.sub.2 H.sub.4 OH                                                                      4    3-OCH.sub.3                           NO.sub.2        CO.sub.2 CH.sub.3                                                                      5-CO.sub.2 CH.sub.3                                                                        4    3-OCH.sub.3                           SCH.sub.3       CO.sub.2 C.sub.2 H.sub.5                                                               5-CN        3,4  H                                     CHO             CO.sub.2 C.sub.2 H.sub.5                                                               5-CN        4    2-NHC.sub.6 H.sub.5                   COOCH.sub.3     H       4-OC.sub.2 H.sub.5                                                                         2    5-NHCOCH.sub.3                        H               CN      5-CN        3,4  H                                     SO.sub.2 C.sub.6 H.sub.5                                                                       H       4-SO.sub.2 C.sub.6 H.sub.5                                                                 2    5-CONHC.sub.4 H.sub.9n                SO.sub.2 C.sub.6 H.sub.5                                                                       H       4-CH.sub.3  2    5-C.sub.6 H.sub.11                    SO.sub.2 C.sub.6 H.sub.4p-Cl                                                                   H       4-SO.sub.2 C.sub.6 H.sub.4p-Cl                                                             2    5-OC.sub.6 H.sub.5                    SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                             H       4-SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                       2    5-SCH.sub.3                           SO.sub.2 C.sub.6 H.sub.4m-OCH.sub.3                                                            SO.sub.2 C.sub.6 H.sub.11                                                              4-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                      2    5-SC.sub.6 H.sub.5                    SO.sub.2 CH.sub.2 CH.sub.2 CN                                                                  H       4-SO.sub.2 CH.sub.2 CH.sub.2 CN                                                            2    5-NHCOOCH.sub.3                       SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              H       4-SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                        2    5-NHSO.sub.2 CH.sub.3                  ##STR52##      s-pyridyl                                                                               ##STR53##  2    5-NHCOCH.sub.3                        SC.sub.6 H.sub.11                                                                              H       4-SC.sub.6 H.sub.11                                                                        2    5-NHCOCH.sub.2 Cl                      ##STR54##      NO.sub.2                                                                               H           2    5-NHCOC.sub.2 H.sub.4 OH               ##STR55##      s-pyrimidinyl                                                                          H           2    5-Cl                                   ##STR56##      CN      H           2    5-NHCONHC.sub.2 H.sub.5                ##STR57##      CN                                                                                      ##STR58##  2    5-NHCON(C.sub.2 H.sub.5).sub.2         ##STR59##      COOCH.sub.3                                                                            H           2    5-CH.sub.3                             ##STR60##      CN      H           2    5-NHCOCH.sub.3                         ##STR61##      CN      H           4    H                                     NO.sub.2        H       H           2    5-CH.sub.3                            CN              H       4-CN        2    5-CH.sub.3                            SO.sub.2 CH.sub.2 CH.sub.3                                                                     H       4-SO.sub.2 CH.sub.2 CH.sub.3                                                               2    5-OCH.sub.3                           SO.sub.2 NHCH.sub.3                                                                            H       4-SO.sub.2 CH.sub.3                                                                        2    5-Cl                                  SO.sub.2 CH.sub.3                                                                              H       4-SO.sub.2 CH.sub.3                                                                        2    5-Cl                                  SO.sub.2 C.sub.6 H.sub.5                                                                       H       4-SO.sub.2 C.sub.6 H.sub.5                                                                 4    3-OCH.sub.3                           CN              H       4-Cl        4    3-OCH.sub.3                           SCN             NO.sub.2                                                                               4-Cl        3,4  H                                     CN              H       4-Br        4    2-NHC.sub.6 H.sub.5                   s-pyridyl       CHO     4-OCH.sub.3 2    5-NHCOCH.sub.3                        CN              H       4-CN        3,4  H                                     s-pyrimidinyl   H       4-CN        2    5-CONHC.sub.4 H.sub.9n                CN              CH.sub.3                                                                               4-CN        2    5-C.sub.6 H.sub.11                    CN              Cl      4-CN        2    5-OC.sub.6 H.sub.5                    CN              H       4-CONH.sub.2                                                                               2    5-SCH.sub.3                           CN              H       4-CON(C.sub.2 H.sub.5).sub.2                                                               2    5-SC.sub.6 H.sub.5                    CN              H       4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        2    5-NHCOOCH.sub.3                       CN              H       4-SCN       2    5-NHSO.sub.2 CH.sub.3                 CN              H       4-SCH.sub.3 2    5-NHCOCH.sub.3                        SC.sub.6 H.sub.5                                                                               H       4-CN        2    5-NHCOCH.sub.2 Cl                     SC.sub.4 H.sub.9n                                                                              H       4-CN        2    5-NHCOC.sub.2 H.sub.4 OH              CN              C.sub.6 H.sub.5                                                                        4-CN        2    5-Cl                                  CN              CN      4-CN        2    5-NHCONHC.sub.2 H.sub.5               NO.sub.2        H       H           2    5-NHCON(C.sub.2 H.sub.5).sub.2        __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________      ##STR62##                                                                                                       OH                                           X               Y      Z          Position                                                                            R.sup.2         R.sup.14                __________________________________________________________________________     H               H      H          2    H               6-SO.sub.2                                                                     N(CH.sub.3).sub.2       CH.sub.3        H      H          2    H               6-SO.sub.2                                                                     N(CH.sub.3).sub.2       CN              H      H          2    3-CONH.sub.2    H                       SCH.sub.3       Cl     H          4    H               H                       CN              H      H          4    H               H                       CN              Br     H            2,6                                                                               H               H                       Cl              NO.sub.2                                                                              4-Br       2    H               H                       Br              CHO    4-Br       2    H               6-SO.sub.2                                                                     NHCH.sub.3              SO.sub.2 CH.sub.3                                                                              CN     5-SO.sub.2 CH.sub.3                                                                       2    3-CONH.sub.2    H                       SO.sub.2 CH.sub.3                                                                              H      4-SO.sub.2 CH.sub.3                                                                       2    3-CONHC.sub. 6 H.sub.5                                                                         H                       SO.sub.2 CH.sub.3                                                                              H      4-SO.sub.2 CH.sub.3                                                                       2    3-CONHC.sub.6 H.sub.4p-OC.sub.2                                                H.sub.4 OH      H                       SO.sub.2 C.sub.6 H.sub.5                                                                       H      H          4    H               H                       SC.sub.2 H.sub.4 OH                                                                            I      H          4    H               H                       SC.sub.6 H.sub.5                                                                               H      4-Cl       4    H               H                       SO.sub.2 C.sub.6 H.sub.5                                                                       H      4-SO.sub.2 C.sub.6 H.sub.5                                                                2    H               H                       CN              SCH.sub.3                                                                             4-CN       2    H               H                       CH.sub.3        NO.sub.2                                                                              H          2    3-CO.sub.2 CH.sub.3                                                                            H                       CN              H      H          2    3-CO.sub.2 CH.sub.3                                                                            H                       OCH.sub.3       SO.sub.2 CH.sub.3                                                                     H            2,4                                                                               H               H                       SC.sub.6 H.sub.4m-CH.sub.3                                                                     SC.sub.6 H.sub.5                                                                      H          2    3-COCH.sub.2 Cl H                       CN              H      H          4    H               H                       C.sub.6 H.sub.5 SC.sub.6 H.sub.11                                                                     H          4    H               H                       CN              H      H          4    H               H                       CN              H      4-CN       4    H               H                       CONH.sub.2      CN     4-CN       4    H               H                       CONHC.sub.2 H.sub.5                                                                            CN     4-CN       2    3-CONHC.sub.6 H.sub.5                                                                          H                       CON(C.sub.2 H.sub.5).sub.2                                                                     CN     4-CN       2    H               H                       CN              H      4-CN       2    3-CONHC.sub.4 H.sub.9n                                                                         H                       CN              SO.sub.2 CH.sub. 3                                                                    4-CN       2    3-CONHC.sub.4 H.sub.9n                                                                         H                       SO.sub.2 CH.sub.3                                                                              H      4-SO.sub.2 CH.sub.3                                                                       2    H               6-SO.sub.2                                                                     N(CH.sub.3).sub.2       SO.sub.2 N(CH.sub.3).sub.2                                                                     SO.sub.2 C.sub.6 H.sub.5                                                              4-SO.sub.2 CH.sub.3                                                                       2    H               6-SO.sub.2                                                                     N(CH.sub.3).sub.2       SO.sub.2 C.sub.4 H.sub.9n                                                                      H      4-SO.sub.2 C.sub.4 H.sub.9n                                                               2    3-CONH.sub.2    H                       SC.sub.2 H.sub.4 OH                                                                            H      4-SC.sub.2 H.sub.4 OH                                                                     4    H               H                       NO.sub.2        CO.sub.2 CH.sub.3                                                                     5-CO.sub.2 CH.sub.3                                                                       4    H               H                       SCH.sub.3       CO.sub.2 C.sub.2 H.sub.5                                                              5-CN         2,6                                                                               H               H                       CHO             CO.sub.2 C.sub.2 H.sub.5                                                              5-CN       2    H               H                       COOCH.sub.3     H      4-OC.sub.2 H.sub.5                                                                        2    H               6-SO.sub.2                                                                     NHCH.sub.3              H               CN     5-CN       2    3-CONH.sub.2    H                       SO.sub.2 C.sub.6 H.sub.5                                                                       H      4-SO.sub.2 C.sub.6 H.sub.5                                                                2    3-CONHC.sub.6 H.sub.5                                                                          H                       SO.sub.2 C.sub.6 H.sub.5                                                                       H      4-CH.sub.3 2    3-CONHC.sub.6 H.sub.4p-OC.sub.2                                                H.sub.4 OH      H                       SO.sub.2 C.sub.6 H.sub.4p-Cl                                                                   H      4-SO.sub.2 C.sub.6 H.sub.4p-Cl                                                            4    H               H                       SO.sub. 2 C.sub.6 H.sub.4p-CH.sub.3                                                            H      4-SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                      4    H               H                       SO.sub.2 C.sub.6 H.sub.4m-OCH.sub.3                                                            SO.sub.2 C.sub.6 H.sub.11                                                             4-SO.sub.2 C.sub.6 H.sub.4p-OCH.sub.3                                                     4    H               H                       SO.sub.2 CH.sub.2 CH.sub.2 CN                                                                  H      4-SO.sub.2 CH.sub.2 CH.sub.2 CN                                                           2    H               H                       SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                              H      4-SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                       2    H               H                        ##STR63##      s-pyridyl                                                                              ##STR64## 2    3-CO.sub.2 CH.sub.3                                                                            H                       SC.sub.6 H.sub.11                                                                              H      4-SC.sub.6 H.sub.11                                                                       2    3-CO.sub.2 CH.sub.3                                                                            H                        ##STR65##      NO.sub.2                                                                              H            2,4                                                                               H               H                        ##STR66##      s-pyrimidinyl                                                                         H          2    3-COCH.sub.2 Cl H                        ##STR67##      CN     H          4    H               H                        ##STR68##      CN                                                                                     ##STR69## 4    H               H                        ##STR70##      COOCH.sub.3                                                                           H          4    H               H                        ##STR71##      CN     H          4    H               H                        ##STR72##      CN     H          4    H               H                       NO.sub.2        H      H          2    3-CONHC.sub.6 H.sub.5                                                                          H                       CN              H      4-CN       2    H               H                       SO.sub.2 CH.sub.2 CH.sub.3                                                                     H      4-SO.sub.2 CH.sub.2 CH.sub.3                                                              2    3-CONHC.sub.4 H.sub.9n                                                                         H                       SO.sub.2 NHCH.sub.3                                                                            H      4-SO.sub.2 CH.sub.3                                                                       2    3-CONHC.sub.4 H.sub.9n                                                                         H                       SO.sub.2 CH.sub.3                                                                              H      4-SO.sub.2 CH.sub.3                                                                       2    H               6-SO.sub.2                                                                     N(CH.sub.3).sub.2       SO.sub.2 C.sub.6 H.sub.5                                                                       H      4-SO.sub.2 C.sub.6 H.sub.5                                                                2    H               6-SO.sub.2                                                                     N(CH.sub.3).sub.2       CN              H      4-Cl       2    3-CONH.sub.2    H                       SCN             NO.sub.2                                                                              4-Cl       4    H               H                       CN              H      4-Br       4    H               H                       s-pyridyl       CHO    4-OCH.sub.3                                                                                 2,6                                                                               H               H                       CN              H      4-CN       2    H               H                       s-pyrimidinyl   H      4-CN       2    H               6-SO.sub.2                                                                     NHCH.sub.3              CN              CH.sub.3                                                                              4-CN       2    3-CONH.sub.2    H                       CN              Cl     4-CN       2    3-CONHC.sub.6 H.sub.5                                                                          H                       CN              H      4-CONH.sub.2                                                                              2    3-CONHC.sub.6 H.sub.4p-OC.sub.2                                                H.sub.4 OH      H                       CN              H      4-CON(C.sub.2 H.sub.5).sub.2                                                              4    H               H                       CN              H      4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       4    H               H                       CN              H      4-SCN      4    H               H                       CN              H      4-SCH.sub.3                                                                               2    H               H                       SC.sub.6 H.sub.5                                                                               H      4-CN       2    H               H                       SC.sub.4 H.sub.9n                                                                              H      4-CN       2    3-CO.sub.2 CH.sub.3                                                                            H                       CN              C.sub.6 H.sub.5                                                                       4-CN       2    3-CO.sub.2 CH.sub.3                                                                            H                       CN              CN     4-CN         2,4                                                                               H               H                       NO.sub.2        H      H          2    3-COCH.sub.2 Cl H                       __________________________________________________________________________

    TABLE 6       ##STR73##        X Y Z R.sup.1 R.sup.2 R.sup.3       H H H C.sub.6 H.sub.5 CH.sub.3 CH.sub.3 CH.sub.3 H H C.sub.6       H.sub.4p-OCH.sub.3 CH.sub.3 CH.sub.3 CN H H C.sub.6 H.sub.5 C.sub.6      H.sub.5 C.sub. 2 H.sub.5 SCH.sub.3 Cl H C.sub.6 H.sub.5 C.sub.6 H.sub.5      CH.sub.3 CN H H C.sub.6 H.sub.4p-OCH.sub.3 C.sub.6 H.sub.5 CH.sub.3 CN      Br H C.sub.6 H.sub.5 C.sub.6 H.sub.5 H Cl NO.sub.2 4-Br C.sub.6 H.sub.5      C.sub.6 H.sub.4p-OCH.sub.3 H Br CHO 4-Br C.sub.6 H.sub.4p-OCH.sub.3      CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 SO.sub.2 CH.sub.3      CN 5-SO.sub.2 CH.sub.3 C.sub.6 H.sub.5 CH(CH.sub.3)C.sub.2 H.sub.5 H      SO.sub.2 CH.sub.3 H 4-SO.sub.2 CH.sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.11      HSO.sub.2 CH.sub.3 H 4-SO.sub.2 CH.sub.3 C.sub.6 H.sub.4p-CH.sub.3      C.sub.6 H.sub.11 C.sub.2 H.sub.5 SO.sub.2 C.sub.6 H.sub.5 H H C.sub.6      H.sub.4p-Cl CH.sub.3 CH.sub.3 SC.sub.2 H.sub.4 OH I H C.sub.6       H.sub.4m-Cl C.sub.6 H.sub.4p-NHCOCH.sub.3 CH.sub.3 SC.sub.6 H.sub.5 H      4-Cl C.sub.6 H.sub.4o-Cl C.sub.6 H.sub.4p-CH.sub.3 CH.sub.3 SO.sub. 2      C.sub.6 H.sub.5 H 4-SO.sub.2 C.sub.6 H.sub.5 C.sub.6 H.sub.4p-Br C.sub.6      H.sub.4m-CH.sub.3 CH.sub.3 CN SCH.sub.3 4-CN C.sub.6 H.sub.4p-NO.sub.2      C.sub.6 H.sub.4m-CH.sub.3 CH.sub.3 CH.sub.3 NO.sub.2 H C.sub.6 H.sub.11      CH.sub.3 CH.sub.3 CN H H CH.sub.2 C.sub.6 H.sub.5 CH.sub.3 CH.sub.3      OCH.sub.3 SO.sub.2 CH.sub.3 H CH.sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5      SC.sub.6 H.sub.4m-CH.sub.3 SC.sub.6 H.sub.5 H C.sub.2 H.sub.5 C.sub.6      H.sub.5 C.sub.2 H.sub.5 CN H H C.sub.6 H.sub.5 C.sub.6 H.sub.5 CH.sub.2      CHCH.sub.2 C.sub.6 H.sub.5 SC.sub.6 H.sub.11 H C.sub.6 H.sub.5 C.sub.6      H.sub.5 CH.sub.2 CH.sub.2 OH CN H H C.sub.6 H.sub.5 CH.sub.2       CH.sub.2OCH.sub.2 CH.sub.2 CN H 4-CN C.sub.6 H.sub.5 CH.sub.2 CH.sub.2      CH.sub.2 CH.sub.2 CH.sub.2 CONH.sub.2 CN 4-CN C.sub.6 H.sub.5  CH.sub.2      C.sub.6 H.sub.5 C.sub.2 H.sub.5 CONHC.sub.2 H.sub.5 CN 4-CN C.sub.6      H.sub.4p-OCH.sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5 CON(C.sub.2       H.sub.5).sub.2 CN 4-CN C.sub.6 H.sub.4p-OCH.sub.3 C.sub.6 H.sub.5      CH.sub.2 CH.sub.2 OOCCH.sub.3 CN H 4-CN C.sub.6 H.sub.4p-OCH.sub.3      C.sub.4 H.sub.9n C.sub.4 H.sub.9n CN SO.sub.2 CH.sub.3 4-CN C.sub.6      H.sub.4p-OCH.sub.3 C.sub.6 H.sub.11 H SO.sub.2 CH.sub.3 H 4-SO.sub.2      CH.sub.3 C.sub.6 H.sub.4p-OCH.sub.3 CH(CH.sub.3).sub.2 H SO.sub.2      N(CH.sub.3).sub.2 SO.sub.2 C.sub.6 H.sub.5 4-SO.sub.2 CH.sub.3 C.sub.6      H.sub.4p-OH C.sub.6 H.sub.5 C.sub.2 H.sub.5 SO.sub.2 C.sub.4 H.sub.9n H      4-SO.sub.2 C.sub.4 H.sub.9n C.sub.6 H.sub.4p-OH CH.sub.3 CH.sub.3      SC.sub.2 H.sub.4 OH H 4-SC.sub.2 H.sub.4 OH C.sub.6 H.sub.4p-OC.sub.2      H.sub.5 CH.sub.3 CH.sub.3 NO.sub.2 CO.sub.2 CH.sub.3 5-CO.sub.2 CH.sub.3      C.sub.6 H.sub.4p-OCH.sub.2       CH(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 SCH.sub.3 CO.sub.2 C.sub.2 H.sub.5      5-CN C.sub.6 H.sub.4p-OC.sub.6 H.sub.11 CH.sub.3 CH.sub.3 CHO CO.sub.2      C.sub.2 H.sub.5 5-CN C.sub.6 H.sub.4p-CH.sub.2 C.sub.6 H.sub.11 CH.sub.3      CH.sub.3 COOCH.sub.3 H 4-OC.sub.2 H.sub.5 C.sub.6 H.sub.4p-CH.sub.3      C.sub.6 H.sub.5 H H CN 5-CN C.sub.6 H.sub.5 C.sub.6       H.sub.5o,p-di-CH.sub.3 H SO.sub.2 C.sub.6 H.sub.5 H 4-SO.sub.2 C.sub.6      H.sub.5 C.sub.6 H.sub.5 C.sub.6 H.sub.4o-Cl H SO.sub.2 C.sub.6 H.sub.5 H      4-CH.sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.3o,m-di-Cl H SO.sub.2 C.sub.6      H.sub.4p-Cl H 4-SO.sub.2 C.sub.6 H.sub.4p-Cl C.sub.6 H.sub.5 C.sub.6      H.sub.4p-Cl H SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3 H 4-SO.sub.2 C.sub.6      H.sub.4p-CH.sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.4m-CH.sub.3 H SO.sub.2      C.sub.6 H.sub.4m-OCH.sub.3 SO.sub.2 C.sub.6 H.sub.11 4-SO.sub.2 C.sub.6      H.sub.4 p-OCH.sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.4o-OCH.sub.3 H      SO.sub.2 CH.sub.2 CH.sub.2 CN H 4-SO.sub.2 CH.sub.2 CH.sub.2 CN C.sub.6      H.sub.4p-OCH.sub.3 C.sub.6 H.sub.4o-CH.sub.3 H SO.sub.2 CH.sub.2 C.sub.6      H.sub.5 H 4-SO.sub.2 CH.sub.2 C.sub.6 H.sub.5 C.sub.6 H.sub.4p-OCH.sub.3      C.sub.6 H.sub.4m-CH.sub.3 H       ##STR74##       s-pyridyl       ##STR75##       C.sub.6 H.sub.5 H CH.sub.2 CHCH.sub.2  SC.sub.6 H.sub.11 H 4-SC.sub.6      H.sub.11 C.sub.6 H.sub.4p-OCH.sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5       ##STR76##       NO.sub.2 H C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 H       ##STR77##       s-pyrimidinyl H C.sub.6 H.sub.4p-OCH.sub. 3 C.sub.6 H.sub.5 C.sub.2      H.sub.5       ##STR78##       CN H C.sub.6 H.sub.5 C.sub.6 H.sub.4p-CH.sub.3 CH.sub.3       ##STR79##       CN       ##STR80##       C.sub.6 H.sub.5 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 H       ##STR81##       COOCH.sub.3 H C.sub.6 H.sub.5 CH.sub.3 H       ##STR82##       CN H C.sub.6 H.sub.5 C.sub.6 H.sub.4p-CH.sub.2 CH.sub.2 OH H       ##STR83##       CN H C.sub.6 H.sub.4p-NHCOCH.sub.3 C.sub.6 H.sub.5 C.sub.2 H.sub.5      NO.sub.2 H H C.sub.6 H.sub.5 C.sub.6 H.sub.4p-CH.sub.3 H CN H 4-CN      C.sub.6 H.sub.5 C.sub.6 H.sub.4m-NHCOCH.sub.3 H SO.sub.2 CH.sub.2      CH.sub.3 H 4-SO.sub.2 CH.sub.2 CH.sub.3 C.sub.6 H.sub.5 C.sub.6       H.sub.4o-CH.sub.3 H SO.sub.2 NHCH.sub.3 H 4-SO.sub.2 CH.sub.3 C.sub.6      H.sub.5 C.sub.6 H.sub.4m-F H SO.sub.2 CH.sub.3 H 4-SO.sub.2 CH.sub.3      C.sub.6 H.sub.5 C.sub.6 H.sub.4m-CH.sub.3 C.sub.2 H.sub.5 SO.sub.2      C.sub.6 H.sub.5 H 4-SO.sub.2 C.sub.6 H.sub.5 C.sub.6 H.sub.5 C.sub.6      H.sub.4m-OCH.sub.3 H CN H 4-Cl C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5      C.sub.2 H.sub.5 SCN NO.sub.2 4-Cl C.sub.6 H.sub.5 CH.sub.3 CH.sub.3 CN H      4-Br C.sub.6       H.sub.4p-OCH.sub.3 CH.sub.3 CH.sub.3 s-pyridyl CHO 4-OCH.sub.3 C.sub.6      H.sub.5 C.sub.6 H.sub.5 C.sub.2 H.sub.5 CN H 4-CN C.sub.6 H.sub.5      C.sub.6 H.sub.5 CH.sub.3 s-pyrimidinyl H 4-CN C.sub.6 H.sub.4p-OCH.sub.3      C.sub.6 H.sub.5 CH.sub.3 CN CH.sub.3 4-CN C.sub.6 H.sub.5 C.sub.6      H.sub.5 H CN Cl 4-CN C.sub.6 H.sub.5 C.sub.6 H.sub.4p-OCH.sub.3 H CN H      4-CONH.sub.2 C.sub.6 H.sub.4p-OCH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3      CH.sub.2 CH.sub.2 CH.sub.3 CN H 4-CON(C.sub.2 H.sub.5).sub.2 C.sub.6      H.sub.5 CH(CH.sub.3)C.sub.2 H.sub.5 H CN H 4-SO.sub.2 N(C.sub.2       H.sub.5).sub.2 C.sub.6 H.sub.5 C.sub.6 H.sub.11 H CN H 4-SCN C.sub.6      H.sub.4p-CH.sub.3 C.sub.6 H.sub.11 C.sub.2 H.sub.5 CN H 4-SCH.sub.3      C.sub.6 H.sub.4p-Cl CH.sub.3 CH.sub.3 SC.sub.6 H.sub.5 H 4-CN C.sub.6      H.sub.4m-Cl C.sub.6 H.sub.4p-NHCOCH.sub.3 CH.sub.3 SC.sub.4 H.sub.9n H      4-CN C.sub.6 H.sub.4o-Cl C.sub.6 H.sub.4p-CH CH.sub.3 CN C.sub.6 H.sub.5      4-CN C.sub.6 H.sub.4p-Br C.sub.6 H.sub.4m-CH.sub.3 CH.sub.3 CN CN 4-CN      C.sub.6 H.sub.4p-NO.sub.2 C.sub.6 H.sub.4m-CH.sub.3 CH.sub.3 NO.sub.2 H      H C.sub.6       H.sub.11 CH.sub.3 CH.sub.3

                                      TABLE 7                                      __________________________________________________________________________      ##STR84##                                                                     X              Y      Z          R.sup.1                                                                              R.sup.2                                 __________________________________________________________________________     H              H      H          CH.sub.3                                                                             H                                       CH.sub.3       H      H          C.sub.4 H.sub.9n                                                                     H                                       CN             H      H          C.sub.3 H.sub.7n                                                                     CH.sub.3                                SCH.sub.3      Cl     H          C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                         CN             H      H          Ph    C.sub.6 H.sub.11                        CN             Br     H          OCH.sub.3                                                                            CH.sub.2 Ph                             Cl             NO.sub.2                                                                              4-Br       OC.sub.3 H.sub.7n                                                                    CH.sub.2 CH.sub.2 OH                    Br             CHO    4-Br       H     Php-Cl                                  SO.sub.2 CH.sub.3                                                                             CN     5-SO.sub.2 CH.sub.3                                                                       H     Php-CH.sub.3                            SO.sub.2 CH.sub.3                                                                             H      4-SO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             Php-OCH.sub.3                           SO.sub.2 CH.sub.3                                                                             H      4-SO.sub.2 CH.sub.3                                                                       Ph    Ph o,p-di-CH.sub.3                      SO.sub.2 C.sub.6 H.sub.5                                                                      H      H          CH.sub.3                                                                             H                                       SC.sub.2 H.sub.4 OH                                                                           I      H          C.sub.4 H.sub.9n                                                                     H                                       SC.sub.6 H.sub.5                                                                              H      4-Cl       C.sub.3 H.sub.7n                                                                     CH.sub.3                                SO.sub.2 C.sub.6 H.sub.5                                                                      H      4-SO.sub.2 C.sub.6 H.sub.5                                                                C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                         CN             SCH.sub.3                                                                             4-CN       Ph    C.sub.6 H.sub.11                        CH.sub.3       NO.sub.2                                                                              H          OCH.sub.3                                                                            CH.sub.2 Ph                             CN             H      H          OC.sub.3 H.sub.7n                                                                    CH.sub.2 CH.sub.2 OH                    OCH.sub.3      SO.sub.2 CH.sub.3                                                                     H          H     Php-Cl                                  SC.sub.6 H.sub.4m-CH.sub.3                                                                    SC.sub.6 H.sub.5                                                                      H          H     Php-CH.sub.3                            CN             H      H          CH.sub.3                                                                             Php-OCH.sub.3                           C.sub.6 H.sub.5                                                                               SC.sub.6 H.sub.11                                                                     H          Ph    Ph o,p-di-CH.sub.3                      CN             H      H          CH.sub.3                                                                             H                                       CN             H      4-CN       C.sub.4 H.sub.9n                                                                     H                                       CONH.sub.2     CN     4-CN       C.sub.3 H.sub.7n                                                                     CH.sub.3                                CONHC.sub.2 H.sub.5                                                                           CN     4-CN       C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                         CON(C.sub.2 H.sub.5).sub.2                                                                    CN     4-CN       Ph    C.sub.6 H.sub.11                        CN             H      4-CN       OCH.sub.3                                                                            CH.sub.2 Ph                             CN             SO.sub.2 CH.sub.3                                                                     4-CN       OC.sub.3 H.sub.7n                                                                    CH.sub.2 CH.sub.2 OH                    SO.sub.2 CH.sub.3                                                                             H      4-SO.sub.2 CH.sub.3                                                                       H     Php-Cl                                  SO.sub.2 N(CH.sub.3).sub.2                                                                    SO.sub.2 C.sub.6 H.sub.5                                                              4-SO.sub.2 CH.sub.3                                                                       H     Php-CH.sub.3                            SO.sub.2 C.sub.4 H.sub.9n                                                                     H      4-SO.sub.2 C.sub.4 H.sub.9n                                                               CH.sub.3                                                                             Php-OCH.sub.3                           SC.sub.2 H.sub.4 OH                                                                           H      4-SC.sub.2 H.sub.4 OH                                                                     Ph    Pho,p-di-CH.sub. 3                      NO.sub.2       CO.sub.2 CH.sub.3                                                                     5-CO.sub.2 CH.sub.3                                                                       CH.sub.3                                                                             H                                       SCH.sub.3      CO.sub.2 C.sub.2 H.sub.5                                                              5-CN       C.sub.4 H.sub.9n                                                                     H                                       CHO            CO.sub.2 C.sub.2 H.sub.5                                                              5-CN       C.sub.3 H.sub.7n                                                                     CH.sub.3                                COOCH.sub.3    H      4-OC.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                         H              CN     5-CN       Ph    C.sub.6 H.sub.11                        SO.sub.2 C.sub.6 H.sub.5                                                                      H      4-SO.sub.2 C.sub.6 H.sub.5                                                                OCH.sub.3                                                                            CH.sub.2 Ph                             SO.sub.2 C.sub.6 H.sub.5                                                                      H      4-CH.sub.3 OC.sub.3 H.sub.7n                                                                    CH.sub.2 CH.sub.2 OH                    SO.sub.2 C.sub.6 H.sub.4p-Cl                                                                  H      4-SO.sub.2 C.sub.6 H.sub.4p-Cl                                                            H     Php-Cl                                  SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                            H      4-SO.sub.2 C.sub.6 H.sub.4p-CH.sub.3                                                      H     Php-CH.sub.3                            SO.sub.2 C.sub.6 H.sub.4m-OCH.sub.3                                                           SO.sub.2 C.sub.6 H.sub.11                                                             4-SO.sub.2 C.sub.6 H.sub.4m-OCH.sub.3                                                     CH.sub.3                                                                             Php-OCH.sub.3                           SO.sub.2 CH.sub.2 CH.sub.2 CN                                                                 H      4-SO.sub.2 CH.sub.2 CH.sub.2 CN                                                           Ph    Pho,p-di-CH.sub. 3                      SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                             H      4-SO.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                       CH.sub.3                                                                             H                                        ##STR85##     s-pyridyl                                                                              ##STR86## C.sub.4 H.sub.9n                                                                     H                                       SC.sub.6 H.sub.11                                                                             H      4-SC.sub.6 H.sub.11                                                                       C.sub.3 H.sub.7n                                                                     CH.sub.3                                 ##STR87##     NO.sub.2                                                                              H          C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                          ##STR88##     s-pyrimidinyl                                                                         H          Ph    C.sub.6 H.sub.11                         ##STR89##     CN     H          OCH.sub.3                                                                            CH.sub.2 Ph                              ##STR90##     CN                                                                                     ##STR91## OC.sub.3 H.sub.7n                                                                    CH.sub.2 CH.sub.2 OH                     ##STR92##     COOCH.sub.3                                                                           H          H     Php-Cl                                   ##STR93##     CN     H          H     Php-CH.sub.3                             ##STR94##     CN     H          CH.sub.3                                                                             Php-OCH.sub.3                           NO.sub.2       H      H          Ph    Pho,p-di-CH.sub. 3                      CN             H      4-CN       CH.sub.3                                                                             H                                       SO.sub. 2 CH.sub.2 CH.sub.3                                                                   H      4-SO.sub.2 CH.sub.2 CH.sub.3                                                              C.sub.4 H.sub.9n                                                                     H                                       SO.sub.2 NHCH.sub.3                                                                           H      4-SO.sub.2 CH.sub.3                                                                       C.sub.3 H.sub.7n                                                                     CH.sub.3                                SO.sub.2 CH.sub.3                                                                             H      4-SO.sub.2 CH.sub.3                                                                       C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                         SO.sub.2 C.sub.6 H.sub.5                                                                      H      4-SO.sub.2 C.sub.6 H.sub.5                                                                Ph    C.sub.6 H.sub.11                        CN             H      4-Cl       OCH.sub.3                                                                            CH.sub.2 Ph                             SCN            NO.sub.2                                                                              4-Cl       OC.sub.3 H.sub.7n                                                                    CH.sub.2 CH.sub.2 OH                    CN             H      4-Br       H     Php-Cl                                  s-pyridyl      CHO    4-OCH.sub.3                                                                               H     Php-CH.sub.3                            CN             H      4-CN       CH.sub.3                                                                             Php-OCH.sub.3                           s-pyrimidinyl  H      4-CN       Ph    Pho,p-di-CH.sub. 3                      CN             CH.sub.3                                                                              4-CN       CH.sub.3                                                                             H                                       CN             Cl     4-CN       C.sub.4 H.sub.9n                                                                     H                                       CN             H      4-CONH.sub.2                                                                              C.sub.3 H.sub.7n                                                                     CH.sub.3                                CN             H      4-CON(C.sub.2 H.sub.5).sub.2                                                              C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                         CN             H      4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                       Ph    C.sub.6 H.sub.11                        CN             H      4-SCN      OCH.sub.3                                                                            CH.sub.2 Ph                             CN             H      4-SCH.sub.3                                                                               OC.sub.3 H.sub.7n                                                                    CH.sub.2 CH.sub. 2 OH                   SC.sub.6 H.sub.5                                                                              H      4-CN       H     Php-Cl                                  SC.sub.4 H.sub.9n                                                                             H      4-CN       H     Php-CH.sub.3                            CN             C.sub.6 H.sub.5                                                                       4-CN       CH.sub.3                                                                             Php-OCH.sub.3                           CN             CN     4-CN       Ph    Pho,p-di-CH.sub. 3                      NO.sub.2       H      H          CH.sub.3                                                                             H                                       __________________________________________________________________________

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications will be effected within the spirit and scope of the invention. 

We claim:
 1. A dye of the formula ##STR95## wherein X, Y, and Z are independently selected from hydrogen, halogen and cyano, and C is a coupler of the formula ##STR96## wherein R¹, R², R³, R¹⁰, and R¹¹ are independently selected from hydrogen and alkyl, and R⁴ and R⁹ are each selected from hydrogen and phenyl.
 2. A dye according to claim 1 wherein the coupler has the structure ##STR97## wherein R², R⁴, and R⁹ are defined therein.
 3. A dye according to claim 1 wherein the coupler has the structure ##STR98## wherein R⁹ and R¹⁰ are defined therein.
 4. A dye according to claim 1 wherein the coupler has the structure ##STR99## wherein R⁴ and R¹¹ are defined therein.
 5. A dye according to claim 1 wherein the coupler has the structure ##STR100## wherein R¹, R², and R³ are defined therein.
 6. A dye according to claim 1 wherein the coupler has the structure ##STR101## wherein R¹ is defined therein.
 7. A dye according to claim 1 wherein the coupler has the structure ##STR102## wherein R¹ and R² are defined therein.
 8. The dye according to claim 1 having the formula ##STR103##
 9. The dye according to claim 1 having the formula ##STR104##
 10. The dye according to claim 1 having the formula ##STR105##
 11. The dye according to claim 1 having the formula ##STR106##
 12. The dye according to claim 1 having the formula ##STR107## 